JP2014173017A - Inkjet ink for printing and inkjet printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet ink for printing excellent in discharge stability in an inkjet method and light resistance, and capable of easily and surely removing unnecessary dyes by washing when coloring fabrics, and to provide an inkjet printing method excellent in light resistance and capable of manufacturing a printed matter with removing unnecessary dyes in good productivity.SOLUTION: The inkjet ink for printing contains water, a dispersant and a compound represented by the formula (1) as a disperse dye. In the formula (1), where Rrepresents H ot NHCOCH, and Rand Rrepresent each independently OCOCHor CN.

Description

  The present invention relates to an inkjet ink for textile printing and an inkjet textile printing method.

Polyurethane fibers (spandex, elastane) have been rapidly used in recent years due to their excellent stretch elasticity. Due to the comfort and form stability brought by the fit and stretch properties of polyurethane fibers, it is widely used in swimwear, innerwear, socks, sportswear, leisurewear, and so on. In addition, development into formal wear and casual wear is being promoted.
However, when this blend of polyurethane fiber and polyester fiber is dyed with disperse dye, the disperse dye for dyeing the polyester fiber is adsorbed to the polyurethane fiber (it is not a bond as strong as dyeing, so-called white Contamination) and the dye that was not involved in the dyeing remains until the washing process, causing contamination of undyed parts and other fibers.

Conventionally, a method has been proposed for improving dispersibility by removing disperse dyes contaminating polyurethane fibers by devising an auxiliary agent at the time of dyeing or devising a reduction washing condition after dyeing (for example, Patent Document 1, 2). In addition, it has been proposed to use a special dye for the purpose of easy removal by reduction cleaning after dyeing (see, for example, Patent Document 3).
However, even if the above technique is used, unnecessary dyes cannot be sufficiently removed by washing.

JP-A-6-184480 JP 2002-348503 A International Publication No. 10/100972 Pamphlet

  An object of the present invention is to provide an inkjet ink for textile printing that has excellent ejection stability by an inkjet method, excellent light resistance, and can easily and reliably remove unnecessary dyes by washing when dyeing a fabric. Another object of the present invention is to provide an ink-jet printing method capable of producing a printed material having excellent light resistance and from which unnecessary dyes are removed with high productivity.

（式中、Ｒ_１はＨまたはＮＨＣＯＣＨ_３を示し、Ｒ_２およびＲ_３は、それぞれ独立に、ＯＣＯＣＨ_３またはＣＮを示す。）
これにより、インクジェット法による吐出安定性に優れ、耐光性に優れるとともに、布帛を染色する場合に、洗浄による不要な染料の除去を容易かつ確実に行うことができる捺染用インクジェットインクを提供することができる。 Such an object is achieved by the present invention described below.
The inkjet ink for textile printing of the present invention comprises water, a dispersant, and a compound represented by the following formula (1) as a disperse dye.

(In the formula, R ₁ represents H or NHCOCH ₃ , and R ₂ and R ₃ each independently represents OCOCH ₃ or CN.)
Accordingly, it is possible to provide an inkjet ink for textile printing that has excellent ejection stability by an inkjet method, excellent light resistance, and can easily and reliably remove unnecessary dyes by washing when dyeing a fabric. it can.

The inkjet ink for textile printing of the present invention contains at least one of a compound represented by the following formula (2) and a compound represented by the following formula (3) as the compound represented by the above formula (1). preferable.

  Thereby, the discharge stability of the inkjet ink for textile printing by the inkjet method can be made particularly excellent. Further, the ink-jet ink for textile printing and the printed matter produced using the same can be made particularly excellent in light resistance. Moreover, when dyeing | staining a fabric, the removal of the unnecessary dye by washing | cleaning can be performed more suitably, and the white spot contamination in the printed matter manufactured can be prevented more effectively.

In the inkjet ink for textile printing of the present invention, the content of the compound represented by the formula (1) in the inkjet ink for textile printing is preferably 2% by mass or more and 10% by mass or less.
As a result, the fabric can be colored with a sufficient color density, and unnecessary disperse dyes can be more easily removed by washing.

The inkjet ink for textile printing of the present invention preferably contains a formalin condensate of aromatic sulfonic acid as the dispersant.
Thereby, the dispersion stability of the disperse dye represented by the above formula (1) in the inkjet ink for printing is particularly excellent, and the ejection stability of the inkjet ink for printing by the inkjet method is particularly excellent. Can do. Moreover, when dyeing | staining a fabric, the removal of the unnecessary dye by washing | cleaning can be performed more suitably, and the white spot contamination in the printed matter manufactured can be prevented more effectively.

The inkjet ink for textile printing of the present invention preferably contains a polyol having a boiling point of 240 ° C. or higher at 1 atm.
Due to this, ejection failure due to drying of ink solids in the inkjet head nozzles, troubles due to drying and fixing of ink solids in the maintenance system system of the inkjet head cleaning cap, wiper, etc., and further in the ink transport tube in the printer Thus, it is possible to more effectively prevent problems such as clogging due to drying of the ink solid content.

The inkjet ink for textile printing of the present invention preferably contains at least one of diethylene glycol monomethyl ether and triethylene glycol monomethyl ether.
Thereby, the inkjet ink for textile printing can be more effectively infiltrated into the fabric, and the storage stability of the disperse dye during long-term storage can be made particularly excellent.

The inkjet textile printing method of the present invention is a textile textile printing method,
An ink application step for attaching the inkjet ink for textile printing of the present invention to the fabric by an inkjet method;
The fabric includes a polyurethane fiber and a polyester fiber.
Thereby, it is possible to provide an ink-jet printing method that is excellent in light resistance and capable of producing a printed product from which unnecessary dyes are removed with high productivity.

In the inkjet textile printing method of this invention, it is preferable to provide the washing | cleaning process which performs a reduction | restoration washing | cleaning further after the said ink provision process.
This makes it possible to more reliably remove dyes that have not contributed to dyeing (excess dyes) and the like, and more effectively prevent white background contamination in the final printed matter, Stability and fastness can be made particularly excellent. In addition, unintentional discoloration of the fabric can be more effectively prevented.

In the ink jet textile printing method of the present invention, the reduction cleaning is preferably performed by allowing hydrosulfite sodium to act in a hot alkali at 60 ° C or higher.
As a result, dyes that did not contribute to dyeing (excess dyes), pretreatment agents, and the like can be more reliably removed, and white background contamination in the finally obtained printed matter can be more effectively prevented. The color stability and fastness can be further improved. In addition, unintentional discoloration of the fabric can be further effectively prevented. In addition, the productivity of the printed material can be made particularly excellent, and damage to the fabric during the reduction cleaning can be minimized.
The printed material according to the present invention is manufactured using the inkjet ink for printing according to the present invention.
Thereby, while being excellent in light resistance, the printed matter from which the unnecessary dye was removed and the dyeing part of the desired pattern was formed can be provided.

Hereinafter, preferred embodiments of the present invention will be described.
≪Inkjet ink for textile printing≫
First, the inkjet ink for textile printing of the present invention will be described.
The inkjet ink for textile printing of the present invention is ejected by an inkjet method, and includes water, a dispersant, and a compound represented by the following formula (1) as a disperse dye.

（式中、Ｒ_１はＨまたはＮＨＣＯＣＨ_３を示し、Ｒ_２およびＲ_３は、それぞれ独立に、ＯＣＯＣＨ_３またはＣＮを示す。）

(In the formula, R ₁ represents H or NHCOCH ₃ , and R ₂ and R ₃ each independently represents OCOCH ₃ or CN.)

  As a result, the ink jet ink for printing and the printed matter produced using the ink jet ink have excellent light resistance while being excellent in ejection stability by the ink jet method, and are unnecessary by washing when dyeing the fabric. It is possible to easily and reliably remove the dye.

Hereinafter, the components of the inkjet ink for textile printing of the present invention will be described in detail.
[Disperse dye]
The inkjet ink for textile printing of the present invention contains a compound represented by the above formula (1) as a disperse dye.
Such a disperse dye has excellent dispersion stability in inkjet ink for textile printing, and is excellent in ejection stability by the inkjet method. Moreover, it is excellent also in light resistance. Further, when the fabric is dyed, the unnecessary portion which is not dyed on the fabric and is simply adsorbed on the fabric is easily and reliably removed by washing.
In the present invention, the inkjet ink for textile printing may contain a compound represented by the above formula (1) as a disperse dye, and in particular, a compound represented by the following formula (2) and the following formula (3): It is preferable that at least one is included among the compounds represented by this.

  Thereby, the discharge stability of the inkjet ink for textile printing by the inkjet method can be made particularly excellent. Further, the ink-jet ink for textile printing and the printed matter produced using the same can be made particularly excellent in light resistance. Moreover, when dyeing | staining a fabric, the removal of the unnecessary dye by washing | cleaning can be performed more suitably, and the white spot contamination in the printed matter manufactured can be prevented more effectively.

  The content of the compound (dispersed dye) represented by the above formula (1) in the inkjet ink for textile printing is not particularly limited, but is preferably 1% by mass or more and 15% by mass or less. It is more preferable that it is 10% by mass or more. As a result, the fabric can be colored with a sufficient color density, and unnecessary disperse dyes can be more easily removed by washing. On the other hand, if the content of the compound represented by the above formula (1) (disperse dye) is less than the lower limit, the fabric may be colored with a sufficient color density depending on the type of fabric, dyeing conditions, and the like. Can be difficult. In addition, when the content of the compound (dispersed dye) represented by the above formula (1) exceeds the upper limit, the time required for removing unnecessary disperse dyes by washing becomes prominent, and the printed matter Productivity may be reduced. In addition, there is a possibility that the storage stability of the inkjet ink for textile printing and the discharge property of the inkjet head are reduced.

  In addition, the inkjet ink for textile printing of the present invention may contain a plurality of compounds (disperse dyes) represented by the above formula (1). More specifically, the inkjet ink for textile printing of the present invention may contain, for example, a compound represented by the above formula (2) and a compound represented by the above formula (3). Thus, when the inkjet ink for textile printing contains a plurality of compounds represented by the above formula (1), it is preferable that the total content of these compounds satisfies the content.

  Moreover, the inkjet ink for textile printing of the present invention may contain a disperse dye other than the above formula (1) as long as the object of the present invention can be achieved. When a disperse dye other than the compound represented by the above formula (1) is included, the content ratio of the compound represented by the above formula (1) with respect to the total content of the disperse dye contained in the ink is 50 mass on a mass basis. % Or more, preferably 70% by mass or more, and more preferably 90% by mass or more. By setting it as the said range, it can be set as the thing excellent in light resistance.

[water]
The inkjet ink for textile printing of the present invention contains water.
In the inkjet ink for textile printing, water functions as a dispersion medium for dispersing the compound (dispersed dye) as described above.
The content of water in the inkjet ink for textile printing is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 70% by mass or less. Thereby, sufficient storage stability and ejection stability can be secured in a well-balanced manner. On the other hand, if the water content is less than the lower limit, it becomes difficult to ensure the dispersion stability of the disperse dye, and the viscosity of the ink is increased, so that it is difficult to ensure a sufficient discharge amount. Become. Further, if the water content exceeds the upper limit, it becomes difficult to sufficiently add a moisturizing agent necessary for preventing clogging of the ink jet head.

[Dispersant]
The inkjet ink for textile printing of the present invention contains a dispersant.
In the inkjet ink for textile printing, the dispersant exhibits a function of improving the dispersibility of the compound (dispersed dye) as described above.
Examples of the dispersant include an anionic dispersant, a nonionic dispersant, and a polymer dispersant.

  Preferred examples of the anionic dispersant include a formalin condensate of aromatic sulfonic acid. Thereby, the dispersion stability of the disperse dye represented by the above formula (1) in the inkjet ink for printing is particularly excellent, and the ejection stability of the inkjet ink for printing by the inkjet method is particularly excellent. Can do. Moreover, when dyeing | staining a fabric, the removal of the unnecessary dye by washing | cleaning can be performed more suitably, and the white spot contamination in the printed matter manufactured can be prevented more effectively.

  Examples of the “aromatic sulfonic acid” in the formalin condensate of aromatic sulfonic acid include creosote oil sulfonic acid, cresol sulfonic acid, phenol sulfonic acid, β-naphthol sulfonic acid, methyl naphthalene sulfonic acid, butyl naphthalene sulfonic acid and the like. Alkylnaphthalenesulfonic acid, a mixture of β-naphthalenesulfonic acid and β-naphtholsulfonic acid, a mixture of cresolsulfonic acid and 2-naphthol-6-sulfonic acid, and ligninsulfonic acid.

As the anionic dispersant, a formalin condensate of β-naphthalene sulfonic acid, a formalin condensate of alkyl naphthalene sulfonic acid, and a formalin condensate of creosote oil sulfonic acid are preferable.
In addition, the formalin condensate of aromatic sulfonic acid may be contained in the form of an acid in the inkjet ink for textile printing, or may be contained in the form of a salt. In the present specification, these are collectively referred to as “formalin condensate of aromatic sulfonic acid”.

Examples of nonionic dispersants include phytosterol ethylene oxide adducts and cholestanol ethylene oxide adducts.
In the present specification, “phytosterol” means to include both phytosterol and hydrogenated phytosterol. For example, the ethylene oxide adduct of phytosterols includes an ethylene oxide adduct of phytosterol, an ethylene oxide adduct of hydrogenated phytosterol, and the like.

  Similarly, in the present specification, “cholestanol” is meant to include both cholestanol and hydrogenated cholestanol. For example, the ethylene oxide (EO) adduct of cholestanol includes an ethylene oxide adduct of cholestanol, an ethylene oxide adduct of hydrogenated cholestanol, and the like. The amount of ethylene oxide added per mole of phytosterol or cholestanol is preferably 10 mol or more and 50 mol or less and HLB is 13 or more and 20 or less.

Examples of the polymer dispersant include polyacrylic acid partial alkyl esters, polyalkylene polyamines, polyacrylates, styrene-acrylic acid copolymers, vinyl naphthalene-maleic acid copolymers, and the like.
The content of the dispersant in the inkjet ink for textile printing is preferably 0.5% by mass or more and 40% by mass or less, and more preferably 2% by mass or more and 10% by mass or less. Thereby, the dispersion stability of the disperse dye can be made particularly excellent, and the storage stability of the inkjet ink for textile printing can be made particularly excellent.

[Other ingredients]
The inkjet ink for textile printing of the present invention may contain components other than those described above (other components).
Examples of such components include antiseptic / antifungal agents such as benzisoxazoles and benzoisothiazoles, pH adjusters such as triethanolamine, tripropanolamine and adipic acid, chelating reagents such as ethylenediaminetetraacetic acid, Rust preventives such as triazole, UV absorbers, antifoaming agents, surface tension modifiers, polysiloxane compounds, sugars such as trehalose, polyols such as glycerin, diethylene glycol, triethylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, etc. And esters of polyhydric alcohols, emulsifiers, dyes other than the disperse dyes represented by the above formula (1), and the like.

Among them, the inkjet ink for textile printing preferably contains a polyol having a boiling point of 240 ° C. or higher at 1 atm. Due to this, ejection failure due to drying of ink solids in the inkjet head nozzles, troubles due to drying and fixing of ink solids in the maintenance system system of the inkjet head cleaning cap, wiper, etc., and further in the ink transport tube in the printer Thus, it is possible to more effectively prevent problems such as clogging due to drying of the ink solid content.
Specific examples of such polyols having a boiling point of 240 ° C. or higher at 1 atm include glycerin, diethylene glycol, triethylene glycol and the like.

  Further, if the inkjet ink for textile printing contains at least one of diethylene glycol monomethyl ether and triethylene glycol monomethyl ether, it can be sufficiently penetrated into the fabric by adding such glycol ethers to the ink. And the effect that sufficient storage stability is securable without inhibiting the dispersion stability of a disperse dye is acquired.

  Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts. Examples of the organic halogen compound include sodium pentachlorophenol, and examples of the pyridine oxide compound include sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, and isothiazoline-based compounds. Examples of the compound include an amine salt of 1-benzisothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl. -4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4 -Isothiazoline-3-one calcium chloride and the like . Other antiseptic / antifungal agents include sodium dehydroacetate, sodium sorbate, sodium benzoate and the like.

When the inkjet ink for textile printing contains a pH adjuster, the storage stability of the inkjet ink for textile printing can be made particularly excellent. Moreover, the reliability of the printed matter (dyed matter) produced using the inkjet ink for textile printing can be made particularly excellent.
As the pH adjuster, for example, an agent capable of controlling the pH of the inkjet ink for textile printing to a range of 6.0 to 11.0 can be suitably used. Examples of such pH adjusters include alkanolamines such as diethanolamine, triethanolamine, dimethylethanolamine, and diethylethanolamine; alkaline metal water such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide. Examples thereof include oxides; ammonium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate; aminosulfonic acids such as taurine, and adipic acid.

Examples of the chelating reagent include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and the like.
Examples of the antirust agent include acidic sulfites, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and benzotriazole compounds.

Examples of ultraviolet absorbers include benzophenone compounds, cinnamic acid compounds, triazine compounds, stilbene compounds, so-called fluorescent brighteners (compounds that absorb ultraviolet rays typified by benzoxazole compounds), and the like. Is mentioned.
Examples of antifoaming agents include highly oxidized oil compounds, glycerin fatty acid ester compounds, fluorine compounds, silicone compounds, and acetylene compounds.

Examples of the surface tension adjusting agent include a surfactant, and examples thereof include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant.
Examples of the anionic surfactant include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acylmethyl taurate, alkyl sulfate poly Oxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate, diethyl Examples include sulfosuccinate, diethylhexylsylsulfosuccinate, and dioctylsulfosuccinate.

Examples of the amphoteric surfactant include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and others. Examples include imidazoline derivatives.
Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

  Nonionic surfactants include, for example, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and the like. Ether surfactants: polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate Ester surfactants such as rate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne- , 6-diol, 3,5-dimethyl-1-hexyne-3-acetylene glycol (alcohol) based surfactants such as ol.

By including the polysiloxane compound in the inkjet ink for textile printing, it is possible to improve the ejection response of droplet ejection by the inkjet method. Examples of the polysiloxane compound include polyether-modified siloxane and polyether-modified polydimethylsiloxane.
In addition, the surface tension (surface tension at 25 ° C.) of the inkjet ink for textile printing of the present invention is preferably 20 mN / m or more and 50 mN / m or less, and more preferably 25 mN / m or more and 40 mN / m or less. In addition, the surface tension of the inkjet ink for textile printing can be calculated | required by the measurement based on JISK3362 using surface tension meter CBVP-A3 (made by Kyowa Interface Science Co., Ltd.), for example.

  The viscosity (viscosity at 25 ° C.) of the inkjet ink for textile printing of the present invention is preferably 2 mPa · s or more and 20 mPa · s or less. As a result, the ejection stability (e.g., ejection volume stability, droplet flight characteristics) and ejection response (response speed, high frequency compatibility (frequency characteristics), etc.) of the inkjet ink for textile printing are particularly excellent. be able to. In addition, the viscosity of the inkjet ink for textile printing can be calculated | required by the measurement based on JISZ8809 using a vibration-type viscometer.

≪Inkjet printing method≫
Next, the inkjet printing method of the present invention will be described.
The ink-jet printing method of the present invention is a method of printing on a cloth, and includes an ink application step of adhering the ink-jet ink for printing of the present invention as described above to a cloth by an ink-jet method, and the cloth is a polyurethane fiber. And polyester fiber. Thereby, it is possible to provide an ink-jet printing method that is excellent in light resistance and capable of producing a printed product from which unnecessary dyes are removed with high productivity.

  In particular, the inkjet printing method of the present embodiment includes a pretreatment step (1a) for applying a pretreatment agent to a fabric, and an ink applying step for applying the inkjet ink for printing of the present invention as described above to a fabric by an inkjet method. (Recording step) (1b), a heating step (1c) for heat-treating the fabric to which ink has been applied, a washing step (1d) for washing the fabric, and a drying step (1e).

<Pretreatment process>
Prior to the ink application step (recording step) (1b), which will be described in detail later, a pretreatment step is provided (1a). Thus, for example, the ink jet ink for textile printing can be prevented from bleeding at a higher level when the ink jet ink for textile printing is applied to the fabric, and a high-definition image can be recorded (printed) on the fabric.

The pretreatment agent is preferably stable to a high temperature environment in order not to cause contamination due to tarring or the like in the heating step described in detail later. In addition, the pretreatment agent is preferably one that can be easily removed from the fabric in a washing step that will be described in detail later.
As the pretreatment agent used in this step, for example, one containing at least one substance selected from the group consisting of a water-soluble metal salt, a polycation compound, a water-soluble polymer, a surfactant and a water repellent is used. be able to. Thereby, the effect by providing the pre-processing process as mentioned above is exhibited more notably.

  Examples of the water-soluble polymer that can be used for the pretreatment include natural water-soluble polymers and synthetic water-soluble polymers. Examples of natural water-soluble polymers include starches such as corn and wheat, cellulose derivatives such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose, polysaccharides such as sodium alginate, guar gum, tamarind gum, locust bean gum, and gum arabic. Examples include protein substances such as gelatin, casein, and keratin. Examples of the synthetic water-soluble polymer include polyvinyl alcohol, polyvinyl pyrrolidone, and acrylic acid-based polymers.

  Examples of the surfactant that can be used for the pretreatment include anionic, cationic, amphoteric, and nonionic surfactants. Examples of anionic surfactants include higher alcohol sulfates and sulfonates of naphthalene derivatives, and examples of cationic surfactants include quaternary ammonium salts. Examples of the surfactant include imidazoline derivatives, and nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Examples include ethylene oxide adducts of acetylene alcohol.

Examples of the water repellent that can be used for the pretreatment include silicon, fluorine-based and wax-based ones.
The method for applying the pretreatment agent to the fabric is not particularly limited, and for example, an inkjet method, a pad method, a coating method, a spray method, or the like can be suitably used. Thereby, it is possible to prevent bleeding of the textile ink jet ink when the textile ink jet ink is applied to the fabric at a higher level.

The amount of pretreatment agent applied to the fabric is preferably 0.2 parts by mass or more and 50 parts by mass or less, and more preferably 5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the fabric. Thereby, it is possible to prevent bleeding of the textile ink jet ink when the textile ink jet ink is applied to the fabric at a higher level. In addition, when using in combination of several types among the components mentioned above as a pretreatment agent, it is preferable that the sum total of these provision amounts is a value within the said range.
The material constituting the fabric is not particularly limited as long as it contains fibers that can be dyed with disperse dyes, and examples thereof include those containing fibers such as polyester, acetate, triacetate, and polyamide. It may be a blended fiber.

As the fabric, the above-described fibers may be in any form such as woven fabric, knitted fabric, and non-woven fabric. The fabric that can be used in the present invention includes 100% of fibers that can be dyed with disperse dyes, as well as a blended woven fabric or a blended nonwoven fabric with rayon, cotton, polyurethane, acrylic, nylon, wool, silk, etc. Etc. can also be used as textiles for textile printing.
According to the present invention, the occurrence of white-spot contamination can be effectively suppressed and light resistance can be achieved even in a blended fabric that easily causes white-spot contamination (for example, a blended fabric containing polyurethane fiber and polyester fiber). An excellent printed product can be obtained. Further, the thickness of the yarn constituting the fabric as described above is preferably in the range of 10 to 100d.

<Ink application process>
In this step, the textile printing ink-jet ink as described above is applied to the fabric by the ink-jet method (1b).
By adopting the ink jet method, it is possible to easily and reliably form a dyed portion having a fine pattern. In addition, since the ink jet method does not require the use of a plate, it has excellent on-demand characteristics and can be suitably adapted to small-scale production and multi-item production.

As an ink jet method (droplet discharge method), a piezo method, a method of discharging ink by bubbles generated by heating the ink, or the like can be used. From the viewpoint of difficulty, the piezo method is preferable.
The inkjet ink for textile printing can be ejected using a known droplet ejection apparatus.
In this step, a plurality of types of inks may be used. Thereby, for example, the color gamut that can be expressed can be made wider.

<Heating process>
Thereafter, the fabric to which the inkjet ink for textile printing is applied is subjected to a heat treatment (1c). Thereby, the disperse dye contained in the inkjet ink for textile printing can be more firmly adsorbed and fixed to the fabric. As a result, the durability of the printed product finally obtained can be made particularly excellent. Further, the hue inherent in the disperse dye can be more reliably exhibited.

As a heating method in this step, for example, steaming by steam, baking by dry heat, thermosol, HT steamer by superheated steam, HP steamer by pressurized steam, or the like can be employed.
The fabric to which the inkjet ink for textile printing of the present invention is applied may be subjected to heat treatment immediately, or may be subjected to heat treatment after a predetermined time has elapsed.

  The heating temperature in this step is not particularly limited, but is preferably 80 ° C. or higher and 250 ° C. or lower, and more preferably 100 ° C. or higher and 230 ° C. or lower. As a result, the effects of applying the heat treatment as described above can be more remarkably exhibited while more surely preventing unintentional alteration and modification of the constituent materials of the fabric and the inkjet ink for textile printing. Product productivity can be made particularly excellent. In particular, when the fabric includes cotton and silk, the temperature is preferably 100 ° C. or higher and 105 ° C. or lower, and when the fabric includes polyester, the temperature is preferably 160 ° C. or higher and 230 ° C. or lower.

  The heating time in this step is not particularly limited, but is preferably 1 second to 60 minutes and more preferably 1 second to 30 minutes. As a result, the productivity of the printed product can be made particularly excellent while exhibiting the effects of the heat treatment as described above more remarkably. In particular, when the fabric contains cotton and silk, it is preferably 5 minutes or longer and 30 minutes or shorter, and when the fabric contains polyester, it is preferably 1 second or longer and 60 minutes or shorter.

  In this step, a carrier may be used. The compound used as the carrier is preferably a compound having characteristics such as large dyeing acceleration, simple use, stable, low burden on human body and environment, easy removal from the fiber, and no influence on dye fastness. Examples of the carrier include phenols such as o-phenylphenol, p-phenylphenol, methylnaphthalene, alkyl benzoate, alkyl salicylate, chlorobenzene and diphenyl, ethers, organic acids, hydrocarbons and the like. By using such a carrier in combination with a disperse dye as described above, the dyeability can be made particularly excellent. That is, normally, the swelling and plasticization of difficult-to-dye fibers that are difficult to dye at around 100 ° C. such as polyester are promoted, and the disperse dyes easily enter the fibers. The carrier may be preliminarily adsorbed on the fabric fibers to which the inkjet ink for textile printing is applied, or may be contained in the inkjet ink for textile printing. Further, it may be applied to the fabric after the inkjet ink for textile printing is applied.

<Washing process>
The ink jet textile printing method of the present embodiment includes a cleaning process (reducing cleaning process) for performing reducing cleaning. This makes it possible to more reliably remove dyes that do not contribute to dyeing (excess dyes), pre-treatment agents, and the like, and more effectively prevent white background contamination in the finally obtained printed matter. And the color stability and fastness can be made particularly excellent. In addition, unintentional discoloration of the fabric can be more effectively prevented.

The reduction cleaning may be performed by causing the composition containing the reducing agent to act on the fabric to which the above-described disperse dye is applied.
Examples of the reducing agent include hydrosulfite sodium, thiourea dioxide, longalit C (sodium formaldehyde sulfoxylate), longalit CL, longalit Z (zinc formaldehyde sulfoxylate) and the like.

  In particular, the reduction cleaning is preferably performed by allowing hydrosulfite sodium as a reducing agent to act in a hot alkali at 60 ° C. or higher. As a result, dyes that did not contribute to dyeing (excess dyes), pretreatment agents, and the like can be more reliably removed, and white background contamination in the finally obtained printed matter can be more effectively prevented. The color stability and fastness can be further improved. In addition, unintentional discoloration of the fabric can be further effectively prevented. Further, the productivity of the printed material can be made particularly excellent.

The content of the reducing agent in the composition used for the reduction cleaning (composition containing the reducing agent) is preferably 0.1% by mass or more and 2% by mass or less, and is 0.2% by mass or more and 1% by mass or less. More preferably.
As the alkali, for example, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate and the like can be used, and sodium hydroxide is particularly preferable.

Further, the composition containing a reducing agent is preferably a solution (particularly an aqueous solution) containing a surfactant in addition to the above components. Thereby, it is possible to more efficiently reduce excess dye by impregnating the fabric fibers with the reducing agent more efficiently.
In addition, the treatment time when performing the reduction cleaning as described above is preferably 1 minute or more and 120 minutes or less, and more preferably 10 minutes or more and 60 minutes or less.

As a method for applying the composition containing the reducing agent to the cloth to which the disperse dye is applied, for example, a continuous type such as an open soaper, a batch type using a liquid dyeing machine, or the like can be employed.
In this step, in addition to the above reduction cleaning, water washing (including hot water washing) may be performed. Moreover, in this process, you may perform the process using dye fixing agents, such as a fix processing agent. Thereby, washing fastness can be improved. As the fix treatment agent, for example, polyamine compounds, dicyandiamide compounds, quaternary ammonium salt compounds, and the like can be used.

<Drying process>
Thereafter, the desired printed matter is obtained by drying.
Drying can be performed by squeezing or dehydrating the washed fabric and then drying or using a dryer, heat roll, iron, or the like.

≪Prints≫
Next, the printed material according to the present invention will be described.
The printed matter according to the present invention is produced using the above-described inkjet ink for printing according to the present invention. Thereby, while being excellent in light resistance, the printed matter from which the unnecessary dye was removed and the dyeing part of the desired pattern was formed can be provided.
The printed material according to the present invention may be used for any purpose, and examples thereof include clothing such as T-shirts and trainers, and banners.

As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.
For example, in the above-described embodiment, the case where the pretreatment process, the ink application process (recording process), the heating process, the cleaning process, and the drying process are representatively described, but the inkjet printing method of the present invention is described. As long as it has an ink application step for attaching the inkjet ink for textile printing of the present invention to a fabric by an inkjet method, the other steps may be omitted.
Moreover, in the inkjet textile printing method of this invention, in addition to the process mentioned above, you may have another process. For example, the ink jet textile printing method of the present invention may have a winding process for winding the fabric between the ink application process and the heating process.

[1] Preparation of inkjet ink for textile printing Ink-jet ink for textile printing was prepared as follows.
Example 1
Disperse dye of formula (2): 10 parts by mass, formalin condensate of sodium naphthalenesulfonate as a dispersant: 4 parts by mass, sodium lignin sulfonate as a dispersant: 4 parts by mass, and water: 82 parts by mass Parts were subjected to wet grinding with a sand mill for 24 hours in the presence of 100 parts by mass of glass beads to form fine particles. Thereafter, the glass beads were removed by filtration to obtain 100 parts by mass of a dispersion.

  Dispersion: 20 parts by mass, diethylene glycol monomethyl ether: 3 parts by mass, diethylene glycol: 3 parts by mass, glycerin: 20 parts by mass, Plex TR: 1.6 parts by mass, KM-90: 0.03 parts by mass, tripropanol By adding and stirring amine: 0.4 parts by mass, ethylenediaminetetraacetic acid: 0.02 parts by mass, and ion-exchanged water: 51.95 parts by mass, the average particle size of the disperse dye is 120 nm and the disperse dye content is An inkjet ink for textile printing of 2.0% by mass was obtained.

(Examples 2 to 8)
A printing inkjet ink was prepared in the same manner as in Example 1 except that the composition and amount used for the preparation of the inkjet ink for printing were adjusted so that the composition shown in Table 1 was obtained. .

(Comparative Examples 1-4)
A printing inkjet ink was prepared in the same manner as in Example 1 except that the composition shown in Table 1 was obtained by adjusting the type of disperse dye and the amount of each component used.
Table 1 summarizes the compositions of the inkjet inks for textile printing of the above Examples and Comparative Examples.

  In the table, the compound (dispersed dye) represented by the above formula (2) is represented by “D1”, the compound represented by the above formula (3) (dispersed dye) is represented by “D2”, and represented by the following formula (4). The compound (dispersed dye) obtained is represented by “D3”, the compound represented by the following formula (5) (dispersed dye) is represented by “D4”, C.I. I. Disperse thread 153 (disperse dye) is changed to “D′ 1”, C.I. I. Disperse Red 302 (disperse dye) is “D′ 2”, formalin condensate of sodium naphthalene sulfonate as a dispersant is “NSF”, sodium lignin sulfonate as a dispersant is “LS”, and diethylene glycol monomethyl ether is “DEGME” ”, Triethylene glycol monomethyl ether as“ TEGME ”, diethylene glycol as“ DEG ”, triethylene glycol as“ TEG ”, glycerin as“ GL ”, and Perex TR as a surfactant (sodium dialkylsulfosuccinate, manufactured by Kao Corporation) "P-TR", Perex CS (sodium dialkylsulfosuccinate, manufactured by Kao Corporation) as a surfactant, "P-CS", Perex SS-L (alkyl diphenyl ether disulfonic acid) as a surfactant Thorium, manufactured by Kao Corporation) as “P-SS-L”, and Perex SS-H as a surfactant (sodium alkyldiphenyl ether disulfonate, manufactured by Kao Corporation) as “P-SS-H” as an antifoaming agent KM-90 (manufactured by Shin-Etsu Silicone) “KM-90”, KM-98 (manufactured by Shin-Etsu Silicone) “KM-98”, Foam Ban MS-455 (Moon) Jing Corporation) “MS-455”, Foam Ban MS-575 as an antifoaming agent (Munsing Corporation) “MS-575”, triethanolamine “TEA”, tripropanolamine “TPA” "Ethylenediaminetetraacetic acid as a chelating agent is indicated by" EDTA ".

  The surface tension at 25 ° C. of the inkjet ink for textile printing of each Example (surface tension obtained by measurement based on JIS K3362 using a surface tension meter CBVP-A3 (manufactured by Kyowa Interface Science Co., Ltd.)) All were included in the range of 25 mN / m or more and 40 mN / m or less. In addition, the viscosity at 25 ° C. (viscosity obtained by measurement according to JIS Z8809 using a vibration viscometer) of the inkjet ink for textile printing of each of the above examples was 2 mPa · s or more and 20 mPa · s. It was included in the following ranges.

[2] Evaluation of ink-jet ink for textile printing [2.1] Storage stability The ink-jet ink for textile printing of each of the above Examples and Comparative Examples was sealed in a polypropylene sample container and allowed to stand in a 60 ° C. environment for 1 week. . The storage stability of the ink was evaluated by observing changes in the viscosity of the ink after standing and the state of separation, sedimentation and aggregation of the ink components. The evaluation criteria are shown below.

[2.1.1] Viscosity change A: The absolute value of the change rate is less than 5% compared to the viscosity immediately after preparation.
B: The absolute value of the rate of change is 5% or more and less than 10% compared to the viscosity immediately after preparation.
C: The absolute value of the change rate is 10% or more and less than 20% compared to the viscosity immediately after preparation.
D: The absolute value of the rate of change is 20% or more compared to the viscosity immediately after preparation.

[2.1.2] Separation / sedimentation / aggregation of components A: There is no separation / sedimentation / aggregation of ink components.
B: Any of separation, sedimentation, and aggregation of ink components is slightly observed.
C: Any of ink component separation / sedimentation / aggregation is clearly seen.
D: Any of ink component separation / sedimentation / aggregation is remarkable.

[2.2] Discharge stability The inkjet ink for textile printing of each of the above examples and comparative examples is an inkjet printer (product name “PX-G930”, manufactured by Seiko Epson Corporation, nozzle resolution: 180 dpi). ) Was filled into the head. After filling, print a nozzle check pattern to confirm that there is no filling failure or nozzle clogging, then turn off the printer and return the head to the home position (ie, capped on the head). And left for 2 weeks in an environment of temperature: 40 ° C. and humidity: 10-20% RH. After leaving, the ink ejection stability was evaluated by performing a cleaning operation as necessary, printing a nozzle check pattern, and observing the state of ink ejection from the nozzles. The evaluation criteria are shown below.

A: Ink was normally ejected from all nozzles within 3 cleaning operations.
B: Ink was normally ejected from all nozzles within the range of 4 to 6 cleaning operations.
C: Ink was normally ejected from all nozzles within the range of 7 to 10 cleaning operations.
D: The cleaning operation was required 11 times or more before ink was normally ejected from all nozzles.

[3] Manufacture of printed matter First, as a fabric, a blend of polyethylene terephthalate fiber and polyurethane fiber is prepared, and carboxymethyl cellulose (water-soluble polymer, fine gum HE, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is prepared. 5.0 parts by mass, 0.3 parts by mass of malic acid (pH adjuster, manufactured by Fuso Chemical Industry Co., Ltd.), 2.0 parts by mass of MS-liquid (reduction inhibitor, manufactured by Meisei Chemical Industry Co., Ltd.) A pretreatment agent in which 92.7 parts by mass of pure water was mixed was applied by an ink jet method to perform pretreatment (pretreatment step). The amount of pretreatment agent applied to the fabric was 20 parts by mass with respect to 100 parts by mass of the fabric.

Next, with respect to the fabric subjected to the pretreatment as described above using an ink jet printer (product name “PX-G930”, manufactured by Seiko Epson Corporation, nozzle resolution: 180 dpi), each of the above examples and comparative examples. The inkjet ink for textile printing was applied in a predetermined pattern (pattern including a colored region and a white background region) (ink application step).
Next, the fabric to which the inkjet ink for textile printing was applied as described above was held in superheated steam at 170 ° C. for 7 minutes (heating step).

Thereafter, washing with water and reduction cleaning were performed (cleaning step). The reduction cleaning is performed by using hydrosulfite sodium as a reducing agent: 1 part by mass, Lucol STA as a surfactant (manufactured by Meisei Chemical Co., Ltd.): 0.5 part by mass, and sodium hydroxide: 0.5 part by mass. Part and water: 150 parts by mass were used under the conditions of treatment temperature: 80 ° C. and treatment time: 30 minutes.
Then, it dried at 60 degreeC over 2 hours, and obtained the printed matter (drying process).

[4] Evaluation of printed matter [4.1] Evaluation of white spot contamination For the printed matter of each Example and Comparative Example manufactured in [3] above, the degree of contamination of the white background area after the cleaning process was evaluated according to the following criteria. did.
A: The hue change ΔE of the white background area before and after washing is less than 5, and no difference can be confirmed with the naked eye.
B: The hue change ΔE of the white background before and after washing is less than 10, and a slight hue change can be confirmed with the naked eye.
C: Hue change ΔE of the white area before and after washing is less than 20, and the hue change can be confirmed with the naked eye.
D: Hue change ΔE in the white area before and after washing is 20 or more, and the hue change can be confirmed with the naked eye.

[4.2] Light fastness The printed matter of each Example and Comparative Example produced in [3] was allowed to stand in a dark place at room temperature for 1 day. After that, the evaluation sample was placed in a Xenon light resistance tester XL-75s (trade name: manufactured by Suga Test Instruments Co., Ltd.), and a 14-day exposure test was performed under the conditions of 23 ° C. relative humidity 50% RH and illuminance 75000 lux. It was.
Then, the spectrophotometer Spectrolino (trade name, manufactured by GretagMacbeth) was used to measure the OD value before and after the light irradiation of the dyed portion of the printed product. The OD value was measured at a viewing angle of 2 ° with a light source of D50, no light source filter, and absolute white as a white standard.

  In addition, evaluation of light resistance was performed by calculating | requiring the optical density residual ratio (Relic Optical Density: ROD) of the image of each printed matter after light irradiation from the obtained measured value (OD value). The calculation method of ROD is “ROD (%) = (Dn / Do) × 100 (where Dn is the OD value of the image after the end of the light irradiation test, and Do is the OD value of the image before the start of the light irradiation test)”. It is. A higher ROD value indicates less degradation of the image due to light irradiation.

The evaluation criteria for light resistance are as follows. If the evaluation criteria are “A” and “B”, it can be determined that the light resistance is practically usable.
A: ROD is 80% or more.
B: ROD is 70% or more and less than 80%.
C: ROD is 60% or more and less than 70%.
D: ROD is less than 60%.
These results are shown in Table 2.

  As is clear from Table 2, satisfactory results were obtained with the present invention, whereas satisfactory results were not obtained with the comparative example.

Claims (8)

An inkjet ink for textile printing comprising water, a dispersant, and a compound represented by the following formula (1) as a disperse dye.

(In the formula, R ₁ represents H or NHCOCH ₃ , and R ₂ and R ₃ each independently represents OCOCH ₃ or CN.) The inkjet ink for textile printing according to claim 1, comprising at least one of a compound represented by the following formula (2) and a compound represented by the following formula (3) as the compound represented by the formula (1). .

  The inkjet ink for textile printing of Claim 1 or 2 whose content rate of the compound represented by said Formula (1) in the inkjet ink for textile printing is 2 mass% or more and 10 mass% or less.   The inkjet ink for textile printing according to any one of claims 1 to 3, comprising a formalin condensate of aromatic sulfonic acid as the dispersant.   The inkjet ink for textile printing according to any one of claims 1 to 4, wherein the inkjet ink for textile printing contains a polyol having a boiling point of 240 ° C or higher at 1 atm.   The inkjet ink for printing according to any one of claims 1 to 5, wherein the inkjet ink for textile printing contains at least one of diethylene glycol monomethyl ether and triethylene glycol monomethyl ether. A method for printing on a fabric,
An ink application step for attaching the inkjet ink for textile printing according to any one of claims 1 to 6 to the fabric by an inkjet method,
An ink-jet printing method, wherein the fabric contains polyurethane fiber and polyester fiber.   The ink jet textile printing method according to claim 7, further comprising a cleaning step of performing reduction cleaning after the ink application step.